Chemical Approaches to the Design of Oxide Materials.

Chemical methods of synthesis play a crucial role in designing and discovering new and novel materials and in providing less cumbersome methods for preparing known materials. Chemical methods also enable the synthesis of metastable materials which are otherwise difficult to prepare. In this presentation, the various innovative chemical methods of synthesising oxide materials will be briefly reviewed with emphasis on soft-chemical routes. Electrochemical synthesis, ion-exchange method, alkali-flux method and some of the interaction reactions will be highlighted, besides topochemical aspects of solid state synthesis. Cuprate superconductors as well as intergrowth structures will also be examined.

Conformation of polymerizable diacetylenic lecithin, DC8,9PC, by 1H-NMR spectroscopy

Diacetylenic phospholipid, 1,2 bis-(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine (DC8,9PC), forms helices and tubules in addition to liposomes. The diacetylenic moiety responsible for the transformation is probed by 2-D NMR correlated spectroscopy. Chemical shift assignments and the analysis of 2D-COSY measurements were done on the lipid in chloroform-d solution. Based on this analysis, a model for the lipid is proposed. The geometry of the headgroup, glycerol backbone and acyl chains up to three methylenes from glycerol backbone [-(CH2)(3)-] is similar to that of dipalmitoyl phosphatidylcholine. The estimated torsional angle for methylene groups adjacent to diacetylenic moieties suggested an overall tilt of the diacetylenic lipid molecule from the bilayer axis of 25-30 degrees. This tilt could be negative or positive depending on the handedness of the resultant microstructures.

Composition Driven Monolayer to Bilayer Transformation in a Surfactant Intercalated Mg-Al Layered Double Hydroxide

The structure and organization of dodecyl sulfate (DDS) surfactant chains intercalated in an Mg-Al layered double hydroxide (LDH), Mg(1-x)Alx(OH)(2), with differing Al/Mg ratios has been investigated. The Mg-Al LDHs can be prepared over a range of compositions with x varying from 0.167 to 0.37 and therefore provides a simple system to study how the organization of the alkyl chains of the intercalated DDS anions change with packing density; the Al/Mg ratio or x providing a convenient handle to do so. Powder X-ray diffraction measurements showed that at high packing densities (x >= 0.3) the alkyl chains of the intercalated dodecyl sulfate ions are anchored on opposing LDH sheets and arranged as bilayers with an interlayer spacing of similar to 27 angstrom. At lower packing densities (x < 0.2) the surfactant chains form a monolayer with the alkyl chains oriented flat in the galleries with an interlayer spacing of similar to 8 angstrom. For the in between compositions, 0.2 <= x < 0.3, the material is biphasic. MD simulations were performed to understand how the anchoring density of the intercalated surfactant chains in the Mg-Al LDH-DDS affects the organization of the chains and the interlayer spacing. The simulations are able to reproduce the composition driven monolayer to bilayer transformation in the arrangement of the intercalated surfactant chains and in addition provide insights into the factors that decide the arrangement of the surfactant chains in the two situations. In the bilayer arrangement, it is the dispersive van der Waals interactions between chains in opposing layers of the anchored bilayer that is responsible for the cohesive energy of the solid whereas at lower packing densities, where a monolayer arrangement is favored, Coulomb interactions between the positively charged Mg-Al LDH sheets and the negatively charged headgroup of the DDS anion dominate.

Investigation on the Magnetic Anomaly and the Role of Orbital Moment on the Magnetic Properties of LaMn0.5Co0.5O3

Two distinct ferromagnetic phases are present in LaMn0.5Co0.5O3 for which the spin-only magnetic moment calculated from the high temperature dc susceptibility is found to be unusually high. Such a high moment can only be accounted for by assigning the valence state of the cations to Mn2+-Co4+. This is unrealistic as the earlier report based on X-ray absorption spectroscopy (XAS) has suggested the valence state to be mainly Mn4+-Co2+ with traces of Co3+. Also from our studies using XAS, it is found that the valence state is mainly Mn4+-Co2+. In addition, no notable difference is observed in the minor Co3+ present in both phases. Our results based on X-ray magnetic circular dichroism studies (XMCD) reveal the presence of ``distinct'' high orbital moment associated with Co2+ for both phases. Thus it is found that the distinctness of the orbital moment also plays a vital role in determining the magnetic moment and T-c of both phases of LaMn0.5Co0.5O3. By considering the orbital moment obtained from XMCD, the anomaly in the paramagnetic susceptibility is resolved and thus we are able to assign the valence state to Mn4+-Co2+ configuration. The difference in the magnitude of orbital moment in both phases is believed to be due to the crystal field effects.

Synthesis of Nano Structured Carbon Nitride by Pyrolysis Assisted Chemical Vapour Deposition

Nanostructured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition. A two zone furnace with a uniform temperature over a length of 20 cm in both the zones was built. The precursor Azabenzimidazole (C6H5N3) taken in a quartz tube was evaporated at zone A and pyrolysed at zone B at a temperature of 800 degrees C. The FTIR spectrum of the prepared sample shows peaks at 1272 cm(-1) and 1591 cm(-1) corresponding to C-N stretching and C=N respectively, which confirms the bonding of nitrogen with carbon. Raman D and G peaks are observed at 1357 cm(-1) and 1560 cm(-1) respectively. X-ray photoelectron spectroscopy (XPS) shows the formation of pi bonding between carbon and nitrogen atoms. These observations along with XRD analysis show the formation of crystallites of alpha-C3N4 and beta-C3N4 in the background of graphitic C3N4. The size of the nanocrystals estimated from the SEM images is similar to 100 nm.

Texture Evolution in Boron Modified Ti-6Al-4V Alloy

Owing to their high strength-to-weight ratio, excellent mechanical properties and corrosion resistance, titanium (Ti) and its alloys, especially (alpha+beta) alloys like Ti-6Al-4V is the backbone materials for aerospace, energy, and chemical industries. Trace boron addition (similar to 0.1 wt. %) to the alloy Ti-6Al-4V produces a reduction in as-cast grain size by roughly an order of magnitude resulting in enhanced ductility, higher stiffness, strength and good fracture resistance. Boron addition could also affect the evolution of texture and microstructure in the material. The solidification microstructures of Boron free as well as Boron containing Ti-6Al-4V are found to be almost homogeneous from periphery towards the center of as-cast ingot in terms of both alpha-colony size and distribution. Boron addition substantially reduces alpha-colony size (similar to 50-80 mu m). A gradual change in alpha texture from periphery towards the center has been observed with orientations close to specific texture components suggesting the formation of texture zones. The mechanism of texture evolution can be visualized as a result of variant selection during solidification through (alpha+beta) phase field.

Oxygen-Exchange Reactions Accompanying Oxidation of Vanadyl Sulfate by Diperoxovanadate

The absorption spectrum in the visible range and the, ESR spectrum of vanadyl sulfate were lost on addition of diperoxovanadate. The V-51-NMR spectra revealed that diperoxovanadate was reduced to vanadate and its oligomers. With excess vanadyl, tetrameric vanadate was found to be the major product, During this reaction oxygen was released into the medium. The oxygen-release reaction was inhibited by a variety of organic ligands-imidazole, benzoate, formate, mannitol, ethanol, Tris, DMPO, malate, and asparagine. An oxygen-consuming reaction emerged at high concentrations of some of these compounds, e.g. benzoate and ethanol. Using DMPO as the spin-trap, an oxygen-radical species with a 1:2:2:1 type of ESR spectrum was detected in the reaction mixtures resulting from vanadyl oxidation by diperoxovanadate which was unaffected by addition of catalase or ethanol. The results showed that secondary oxygen-exchange reactions occur which depend on and utilize the intermediates in the primary reaction during diperoxovanadate-dependent oxidation of vanadyl sulfate.

Chemical Synthesis of Metal Nanoparticles Using Amine-Boranes

The development of new synthetic strategies to obtain mono-disperse metal nanoparticles on large scales is an attractive prospect in the context of sustainability. Recently, amine-boranes, the classical Lewis acid-base adducts, have been employed as reducing agents for the synthesis of metal nanoparticles. They offer several advantages over the traditional reducing agents like the borohydrides; for example, a much better control of the rate of reduction and, hence, the particle size distribution of metal nanoparticles; diversity in their reducing abilities by varying the substituents on the nitrogen atom; and solubility in various protic and aprotic solvents. Amine-boranes have not only been used successfully as reducing agents in solution but also in solventless conditions, in which along with the reduction of the metal precursor, they undergo in situ transformation to afford the stabilizing agent for the generated metal nanoparticles, thereby bringing about atom economy as well. The use of amine boranes for the synthesis of metal nanoparticles has experienced an explosive growth in a very short period of time. In this Minireview, recent progress on the use of amine boranes for the synthesis of metal nanoparticles, with a focus towards the development of pathways for sustainability, is discussed.

Soft-chemical routes to synthesis of solid oxide materials

We describe three different families of metal oxides, viz., (i) protonated layered perovskites, (ii) framework phosphates of NASICON and KTiOPO4 (KTP) structures and (iii) layered and three-dimensional oxides in the H-V-W-O system, synthesized by 'soft-chemical' routes involving respectively ion-exchange, redox deinteracalation and acid-leaching from appropriate parent oxides. Oxides of the first family, HyA2B3O10(A = La/Ca; B = Ti/Nb), exhibit variable Bronsted acidity and intercalation behaviour that depend on the interlayer structure. V2(PO4)3 prepared by oxidative deintercalation from Na3V2(PO4)3 is a new host material exhibiting reductive insertion of lithium/hydrogen, while K0.5Nb0.5 M0.5OPO4(M = Ti, V) are novel KTP-like materials exhibiting second harmonic generation of 1064 nm radiation. HxVxW1-xO3 for x = 0.125 and 0.33 possessing alpha-MoO3 and hexagonal WO3 structures, prepared by acid-leaching of LiVWO6, represent functionalized oxide materials exhibiting redox and acid-base intercalation reactivity.

Soft chemical synthesis of new layered and three-dimensional oxide hydrates, hxVxW1-xO3×yH2O, related to WO3×2 H2O and WO3. times.1/3 H2O

Two new vanadium-tungsten oxide hydrates of the formulas, H0.125V0.125W0.875O3.1.5H2O (I) and Ho.33V0.33W0.67O3.1/3H2O (II), have been synthesized by acid-leaching of LiVWO6 with aqueous HNO3/HCl. While phase I obtained by treatment of LiVWO6 with dilute HNO3/HCl possesses an orthorhombic structure (a = 7.77(3), b = 13.87(6), c = 7.44(3) angstrom) related to WO3.2H2O, phase II, prepared by refluxing LiVWO6 with concentrated HNO3, is isostructural with WO3.1/3H2O. Dehydration of II around 330-degrees-C yields a hexagonal phase (III, a = 7.25(4), c = 7.74(3) angstrom) isotypic with hexagonal WO3. Both land III exhibit redox and acid-base intercalation reactivity characteristic of layered and tunnel structures.

Soft-chemical synthesis of new non-linear optical materials, K0.5M0.5Ti0.5OPO4(M = Nb, Ta),related to KTiOPO4

Soft-chemical oxidation of KTiOPO4-like KM(0.5)(V)Ti(0.5)(III)OPO(4) (M = Nb, Ta) using chlorine in CHCl3 is accompanied by partial deintercalation of potassium, yielding K(0.5)MV(0.5)Ti(0.5)(IV)OPO(4) compounds which are new non-linear optical materials that exhibit efficient second-harmonic generation of 1064 nm radiation, as does KTiOPO4.

Thermodynamic and structural consequences of changing a sulfur atom to a methylene group in the M13Nle mutation in ribonuclease-S

Two fragments of pancreatic ribonuclease A, a truncated version of S-peptide (residues 1-15) and S-protein (residues 21-124), combine to give a catalytically active complex. We have substituted the wild-type residue at position 13, methionine (Met), with norleucine (Nle), where the only covalent change is the replacement of the sulfur atom with a methylene group. The thermodynamic parameters associated with the binding of this variant to S-protein, determined by titration calorimetry in the temperature range 10-40 degrees C, are reported and compared to values previously reported [Varadarajan, R., Connelly, P. R., Sturtevant, J. M., & Richards, F. M. (1992) Biochemistry 31, 1421-1426] for other position 13 analogs. The differences in the free energy and enthalpy of binding between the Met and Nle peptides are 0.6 and 7.9 kcal/mol at 25 degrees C, respectively. These differences are slightly larger than, but comparable to, the differences in the values for the Met/Ile and Met/Leu pairs. The structure of the mutant complex was determined to 1.85 Angstrom resolution and refined to an R-factor of 17.4% The structures of mutant and wild-type complexes are practically identical although the Nle side chain has a significantly higher average B-factor than the corresponding Met side chain. In contrast, the B-factors of the atoms of the cage of residues surrounding position 13 are all somewhat lower in the Nle variant than in the Met wild-type. Thus, the large differences in the binding enthalpy appear to reside entirely in the difference in chemical properties or dynamic behavior of the -S- and -CH2- groups and not in differences in the geometry of the side chains or the internal cavity surface. In addition, a novel method of obtaining protein stability data by means of isothermal titration calorimetry is introduced.

Constructions of 2D-Metallamacrocycles Using Half-Sandwich Ru-2(II) Precursors: Synthesis, Molecular Structures, and Self-Selection for a Single Linkage Isomer

Coordination-driven self-assembly of oxalato-bridged half-sandwich p-cymene ruthenium complex Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)] (O3SCF3)(2) (1a) with several ditopic donors (L-a-L-d) in methanol affords a series of bi- and tetranuclear metallamacrocycles (2a and 3-5). Similarly, the combination of 2,5-dihydroxy-1,4-benzoquinonato (dhbq)-bridged binuclear complex Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) with a flexible bidentate amide linker (L-a) in 1:1 molar ratio gave the corresponding tetranuclear complex 2b. All the macrocycles were isolated as their triflate salts in high yields and were fully characterized by various spectroscopic techniques. Finally, the molecular structures of all the assemblies were determined unambiguously by single-crystal X-diffraction analysis. Interestingly, the combination of acceptor 1a or 1b with an unsymmetrical linear ditopic donor L-a results in a self-sorted linkage isomeric (head-to-tail) macrocycle (2a or 2b) despite the possibility of formation of two different isomeric macrocycles (head-to-head or head-to-tail) due to different connectivity of the donor. Molecular structures of the complexes 2a and 2b showed tetranuclear rectangular geometry with dimensions of 5.51 angstrom x 13.29 angstrom for 2a and 7.91 angstrom x 13.46 angstrom for 2b. In both cases, two binuclear Ru-2(II) building blocks are connected by a mu-N-(4-pyridyl)isonicotinamide donor in a head-to-tail fashion. Surprisingly, the macrocycle 2a loses one counteranion and cocrystallizes with monodeprotonated 1,3,5-trihydroxybenzene via strong intermolecular pi-pi stacking and hydrogen bonding. The tweezer complex 3 showed strong fluorescence in solution, and it showed fluorescence sensing toward nitroaromatic compounds. A fluorescence study demonstrated a marked quenching of the initial fluorescence intensity of the macrocycle 3 upon gradual addition of trinitrotoluene and exhibits significant fluorescence quenching response only for nitroaromatic compounds compared to various other aromatic compounds tested.

Wet chemical syntheses of ultrafine multicomponent ceramic powders through gel to crystallite conversion

Coarse (BOn/2)-O-n+/xH(2)O (10